Catalytic process fob polymeriz



Patented Sept. 3, 1940 v v CATALYTIC PROCESS FOR P OLYMIERJZ- ING FATTY OILS Samuel 0. Sorensen and James C. Konen, Minneapolis, Minn., assignors to Archer-Daniels-Midland Company, a corporation of Delaware No Drawing. Application July 21, 1938,

Serial No. 220,512

12 Claims. (Cl. 260--407) This invention relates to a catalytic process such as cost, efiect on color, and acceleration of for polymerizing oils and more particularly to the polymerization of'the oil. For some uses, the polymerization catalysts used therein. such as in dark colored enamels or inks, the

Vegetable oils, such as linseed oil, are polycolor retention is not so important as bodying merized by heating to high temperatures either speed. In certain light colored products color in an open kettle or under vacuum or pressure retention is of primary importance, although it and with or without the presence of an inert gas. is desirable to have the oil body as rapidly as By these processes the oil is increased in vispossible. cosity to any desired point, even up to a solid Among the useful aromatic compounds we or gelled condition. The polymerized products ve fou d the polycyclic Compounds Containing 10 are called heat bodied oils and are valuable in condensed ring systems of at least three rings to the protective coating, field for use in coatin bethe most effective catalysts There are a compositions, such as enamels, varnishes, printlarge number of such compounds which will acing inks, lacquers, etc. celerate the polymerization of the oils, some of There are many distadvantages to the heat t se e n anthracene, phenanthrene, anthra- 15 bodying processes for oils used heretofore; chief q a aq e diacetate, beta hydrOX among these being the relatively long time needa h q alizarin. ta l a q ed to obtain any substantial viscosity increase 110116, q b fia e hy a I and the darkening in color which the oil under quinolle and -I1itr0anth1&qll1n0ne- App l y 7 goes in heating. There is a certain amount of almost any derivative of anthraqlllnone having 20 decomposition occurring at the high temperatures the anthlaquinone nucleus has an a lera i used and this causes increase in the acid numelfect but substances that include an acidic, 1n-

' her, darkening in color, and excessive loss of oil. organic residue appear to be s va a s in The bodying time can be shorten-ed by increas- Certain P 1510111913 and Should be avoldei mperature, b t th acid number Other aromatic polycyclic compounds which UNITED STATESv PATENT OFFICE,

25 ing the te crease and color darkening are then accelerated, are efiectlve as catalysts, ha e i alpha whi h i .vefy bjegtionab1e nitroso beta naphthol, oxyqulnollne sulrate, 1,2-

Numerous proposals have been made for speednflphthcquinone and lfi-naphthoquinoming up th il bodyjng process by t use of Summing the matter up, it may be stated that so catalysts. For example, it has been claimed that the Substances which are available as certain metal salts of the linoleates, resinates catalysts in accordance with this invention fall or naphthenates when dissolvedin the oil have 111130 the general Class Of the aromatic po ycy c a polymerizing effect upon heating t high t condensed nuclei compounds having at least two peratures. Likewise, it has been stated that rings a d not more than three rings which are certain amine compounds, such as benzidine or substantially free of an acidic inorganic residue. 35 diphenylamine, will also accelerate polymeriza- A particular group in such class is made up of tion. However, these methods all cause excesthe polycyclic condensed nuclei quinone comsive darkening in color of the oil, which usually pounds, and of these we have had particularly makes them more objectionable than if no good results with anthraquinone derivatives of catalyst were usedthe types given above. 40 In accordance with the present invention We The aromatic compound be added to the have discovered a method of accelerating the on in Several ways depending upon the effect polymenzanolt or heat bodymg P 011 that does desired. If the material is soluble in oil at room have P dladYantages mentioned above 1 temperatures, it is simply dissolved in the oil W F mclease the bodymg which can then be polymerized at any time by 45 on mthout damaging the color or causing the usual heat bodying methods. If the catacessive acid number increase. The process comprises the incorporation of relatively small i i 1s not Soluble xcept at hlgh temperatures amounts of certain aromatic compounds in the 5 oil before or during the heat bodying treatment. f' dlssolves as the 01] 1S heated up to body We have discovered that a large number of the mg temperaturesome of the aromatlc aromatic compounds or substances have a stances will dissolve in the oil when heated to sired catalytic effect on polymerization or bodyabout and Will then remain in 80111- ing of oils. In each case the most advantageous tion when the oil is cooled down to room tempermaterial to use depends upon several factors ature. Examples of these are phenanthraqui- 55 none, beta methyl anthraquinone, phenanthrene,

- 1-4 naphthoquinone.

'we flnd that some of the aromatic compounds show a definite accelerating effect on heat bodying when used in amounts of as little as 0.05%. However, we do not wish to confine our invention to either of these limits since they are not always essential. For example, addition of more than 0.5% of the aromatic catalyst will show an increased accelerating effect in, many instances, and the, reasons for using lesser amounts of catalyst are principally the cost of the material and a tendency to darken the color in some cases, particularly if nitrogen is present. In most cases it will be desirable to use not less than about 0.10% and not more than about 0.30% catalyst.

Illustrative but non-limiting examples of oils treated in accordance with the invention are given in the table below. In these tests varying amounts of anthraquinone were added to an alkali refined linseed oil and heated in a one-gallon laboratory kettle at 585 F.

Pei gent coloklngior. v t B11 {8- p0 ymer Z- 5005 i y quinone ing time (polses) catalyst (hours) 0.0 4 103 0. 125 3% 157 0. 25 3? 132 o. a 2 2 10s Analyses of the above oils Nos. 1 and 4 show the following similarities of the polymerized oils:

\ 011 No. l Oil No.4

Iodine number 128. 4 127. 7 Percent unsaponifiable 87 1. 16 Acid num er 5.94 5. 39 specifiqgravitynn 9707 9696 Refractive index 1.4904 11.4900 Molecular weight 1640 1710 These two oils, Nos. 1 and 4, were tested for drying time after the addition of 0.2% Pb and 0.02% of Co driers. The oil No. 4 containing the anthraquinone catalyst dried in three hours and the oil No. 1, containing no catalyst dried in 3 hours.

The percentage of unsaponiflable matter is slightly higher in oil No. 4 because of the addition of the catalyst.

In another example, 0.5% of anthraquinone catalyst was added to an alkali refined soybean oil and comparative heat bodying treatments were made with the same oil without using a catalyst. Both oils were bodied to approximately 100 poises at 585 F. under identical conditions.

The oil containing the anthraquinone catalyst bodied in 6 hours whereas the same oil without the catalyst required 10 hours. The oil bodied with the catalyst was much lighter in color than the oil bodied without catalyst.

Although our invention is of particular value for use with linseed oil because of the wide use of that oil in the protective coating industry, the invention may be used equally well with various other fatty oils including drying and semidrying oils, such as for example, Perilla, hempseed, soybean, sunflower, oils. The use of the aromatic .catalyst is particularly valuable with the slower bodying oils which normally darken. badly before reaching the desired viscosity because of the long cooking time. Here the advantage in speed and color retention by using our invention make the use of slower bodying oils feasible in places where they heretofore could not be used.

The broad class of catalysts that we have found to be particularly useful in this invention comprises the aromatic multiple ring compounds having ten to about twenty-one carbon, atoms and being characterized by the capability of bodying various oils when added thereto in relatively small amounts as described above.

Various modifications and changes may be made in the materials, compositions and method of procedure described hereinabove without departing from the scope of our invention, some of the novel features of which are defined in the appended claims.

We claim:

1. In a process for heat bodying oils of the class of drying and semi-drying oils, the improvement which comprises using as a catalyst anthraquinone in sufficient proportion to have a substantial catalytic effect upon the bodying of the oil during heating.

2. In a process for heat bodying fatty oils, the improvement which comprises using as a catalyst an anthraquinone derivative having the anthraquinone nucleus but which is substantially free of an acidic inorganic residue in suiiicient proportion to have a substantial catalytic effect upon the bodying of the oil during heating.

3. In a process for heat bodying fatty oils, the

improvement which comprises using as a catalyst approximately 0.05% to 0.5% of beta-methyl anthraquinone in sufiicient proportion to have a substantial catalytic effect upon the bodying of the oil during heating.

4. Ina process for heat bodying oils of the class of drying and semi-drying oils, the improvement which comprises using as a catalyst approximately 0.05% to 0.5% of beta chloranthraquinone in suflicient proportion to have a substantial catalytic effect upon the bodying of the oil during heating.

5. An oil of the class of drying and semi-drying oils adapted to be bodied by heat and containing as bodying catalyst approximately 0.05% to 0.5% of anthraquinone in sufiicient proportion to have a substantial catalytic effect upon the bodying of the oil during heating.

6. In a process for heat bodying oils of the class of drying and semi-drying oils, the improvement =phenanthraquinone, beta methyl anthraquinone and nitroanthraquinone.

7. In a fatty oil adapted to be bodied by heat a catalyst comprising an aromatic, polycyclic, condensed nucleic compound having at least two rings and not more than three rings and being substantially free of an acidic inorganic residue, said compound being present in sufiicient proportion to have a substantial catalytic efiect upon the bodying of the oil during heating.

8. A fatty oil-catalyst substance as defined in claim '7 in which the oil is of the class of drying and semirdrying oils. 9. A fatty oil-catalyst substance as defined in claim 7 in which the amount of about 0.05%

the Oil.

catalyst is present in an to 0.5% of the weight of 10. A fatty oil-catalyst substance as defined in 5 claim 7 in which the catalyst compound has between 10 and 15 carbon atoms.

11. A fatty oil adapted to be bodied by heat and containing as a bodying catalyst an aromatic,

polycyclic, condensed nuclei quinone compound 10 which is substantially free of an acidic inorganic residue, said compound being present in sumcient SAMUEL o. SORENSEN. JAMES c. KONEN'. 

